Crocodile: Get the "Top Pirate of the Continent" rank to unlock Crocodile as a captain in Grand Adventure mode.

Chaser: Reach level 15 with him in Chaser's adventure, then win a battle using him.

Chaser (Smoker): Get the "Top Pirate of the Grand Line" rank to unlock Chaser (Smoker) as a captain in Grand Adventure mode.

Buggy: Get the "Top Pirate of the Island" rank to unlock Buggy as a captain in Grand Adventure mode.

Eneru: In Adventure mode as Crocodile, get Eneru as an ally in the Jaya area. Then, win a battle using him.

Kuina: In Adventure mode as Chaser, recruit Kuina in the ship graveyard. Then, defeat Zolo using her in Alabasta.

Mihawk: In Adventure mode as Chaser (Smoker), get Mihawk as an ally. Then, win a battle using him.

Mr. 2 Bon Clay: In Adventure mode as Crocodile, get Mr. 2 Bon Clay as an ally. Then, win a battle using him

Nico Robin: In Adventure mode as Luffy, get Nico Robin an ally. Then, win a battle using her.

Ohm: In Adventure mode as Crocodile, get Ohm as an ally in the Jaya area. Then, win a battle using him

Shanks: In Adventure mode as Buggy, get Shanks as an ally. Then, win a battle using him.

Trace (Ace): In Adventure mode as Buggy, recruit Trace in Drum Island. Then, win a battle using him.

Ussop: Defeat the final boss in Adventure mode as Luffy, Buggy, Crocodile, and Chaser in any order.

Zeff: In Adventure mode as Chaser, get Zeff to level 15 and use him once in battle.